Improved mineral lubricating oil composition



United States Patent IMPROVED MINERAL LUBRICATING OIL COMPOSITIUNNo-Drawing. Application September 17, 1956 Serial No. 610,398

2 Claims. (Cl. 252--33.4)

This invention relates to new and improved lubricating compositions,and, more particularly, pertains to detergent mineral lubricating oilcompositions havingincorporated therein'an additive capable ofeffectively reducing oil consumption as well as preventing or at leastmaterially inhibiting wear and corrosion of metals with which theselubricating oil compositions come in contact;

It-iswell known that one of the best additive combinations forimprovingthe properties of lubricating oils particularly with respect todetergency is the combination of an.,oil-soluble sulfonate and anoil-soluble phenate. Although lubricating oils containing these twoadditives possess good detergent properties, they do not protectsufiiciently contacting metal surfaces against wear and corrosion;furthermore, these oils have the defect that their consumption duringuse are normally excessive. Various auxiliary agents, such asarylamines, e.g. phenylalpha-naphthylamine or phenolic compounds, suchas alkyl phenols, have been used with sulfonates and/or phenates in anattempt to overcome some of their deficiencies, but, with littlesuccess.

Ithas now been discovered that lubricating oils containing minor amounts(e.g. from about 0.05% to about 15%, and preferably from about 0.1% toabout 6% by weight) of an oil-soluble polyvalent metal sulfonate and ofan oil-soluble polyvalent metal sulfur-free polyphenate can be greatlyimproved by reducing the depletion rate of the additives by reducing oilconsumption, and by reducing wear as well as corrosion of contactingmetal surfaces, these improvements being obtained by the addition tosuch lubricating oils a minor, but critical, amount of an oil-solublestraight or branched-chain saturated non-aromatic amine and/or amidehaving at least one aliphatic hydrocarbon radical containing from bout12V to 30 carbon atoms, and preferably from 14 to 18 carbon atoms in themolecule; this aliphatic radical is preferably attached directly to anitrogen atom of the amine or amide. The amount of amine which can beused in compositions of this invention can Vary from about 0.01% toabout 0.2% by weight and preferably between 0.05 to 0.1% by weight.

The additives which impart the above desired properties Ito.the"lubricant oils described above may be de fined as oil-soluble straightor branched-chain saturated non-aromatic amines or amides and includeoil-soluble long chain primary secondary or tertiary saturated aliphaticor cycloaliphatic mono or polyamines or amides having at least one alkylradicaloffrom. 12 to 30 carbon atoms inthe molecule. Aliphaticmonoamines of this typeinclude-mono di-, or tri-dodecyl, tetradecyl,hexadecylj-or. octadecyl monoamines. In the secondary and tertiaryamines the alkyl'radicals can be the same or different. Aliphaticpolyamines include alkyl substituted alkylene polyamines wherein thealkylene radical is from 2 to carbon atoms such as ethylene diamine,propylene .diamine, butylene diamine, diethylene tetraamine;tetraethylenepentamine and the alkyl substituent or substituent group(s)can be attached to the same or different nitrogen atoms in the moleculeand should generally have from 12 to 18 carbon atoms. Such alkylsubstituted alkylene polyamines include NC alkyl propylene diamine,N-lauryl propylene diamine and the like. Especially useful are theamines which are commercially available from Armour Chemical Companyunder the trade name of Armeens such as Armeen 18 which is a mixture ofprimary amines predominantly in octadecylamine or Armeen DM18(dimethyloctadecylamine) or Duomeen C NHC H NH The amides includeoil-soluble amides of aliphatic monoand polycarboxylic acids such asmyristic acid, palmitic acid, stearic acid, arachidic acid, behenicacid, soybean oil fatty acid, cocoanut oil fatty acid, succinic acidandmixtures thereof. Preferred amides are stearamide, cocoamide,N,N-dimethyl stearamide, N-lauryl stearamide and mixtures thereof.

Compositions of this invention may be prepared using" any lube oil.Mineral lubricating oils which are particularly desirable for use incompositions of this invention and which have been used as bases for thecompositions of this invention are oils of the SAE SW, 10, 20, 30

5W-20, 5W-30 grades or higher grades obtained from West TexasEllenburger. crudes, East Texas crudes, Oklahoma crudes, or Californiacrudes.

Typical oils of this type are SAE SW and SAE 30 petroleum motor oilshaving the following properties:

The detergent salts which are used in compositions of this inventioninclude sulfonates which can be oil-soluble neutral and/or basicpolyvalent metal petroleum sulfonates, of which petroleum sulfonates ofthe metals of group II of the periodic table having an atomic number offrom 12 to 56, inclusive are preferred, and especially of the alkalineearth metals. the neutral and/ or basic calcium, barium and magnesiumpetroleum sulfonates of oil-soluble petroleum sulfonic acids. The acidscan range in molecular weight from about 350 to 550 and preferably arein the range of from 400 to 500. By basic petroleum sulfonates is meantthat the amount of neutralizing agent, such as calcium carbonate and/orcalcium hydroxide, which is used to neutralize the petroleum sulfonicacid, is in excess of that which is normally required to neutralize theacid. The excess should be from 10 to and preferably between 20 to 60percent of that normally required to neutralize the acid.

The sulfur-free polyphenates used in compositions of thisinvention areoil-soluble neutral and/or basic polyvalent metal sulfur-freepolyphenates. By sulfur-free polyphenate is meant to. include aplurality of phenolic radicals linked together through a carbon, such aswhere a plurality of simple phenates are condensed at positions orthoand/or para to the phenolic hydroxy group through alkylidine (methylene)radicals. The anionic portion ofthe molecule should contain only carbon,hydrogen and oxygenin the molecule. The cationic portion of thepolphenate can be the same as that in the sulfonate and usually-will be,but different cations may be formaldehyde, acetaldehyde or benzaldehyde,e.g, calcium salt of octylphenol-formaldehyde condensation Patented Dec.1, 1959:

Suitable sulfonates include COMPOSITION A Ca salt of octylphenol-formaldehyde condensation product (oil-soluble M.W. 900- 1, 100)0.3% SA. Ca petroleum sulfonate (oil-soluble) 0.1% SA. Octadecylamine0.1% wt. Mineral lubricating oil (SAE 5W) Balance.

1 SA: sulfate ash.

COMPOSITION B Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble) 0.3% SA. Ca petroleum sulfonate (oil-soluble) 0.4% SA.Octadecylamine 0.1% wt. Mineral lubricating oil (SAE 5W) Balance.

COMPOSITION C Ca salt of octyl phenol-formaldehyde (oilsoluble) 0.4% SA.Ba petroleum sulfonate (oil-soluble) 0.3% SA. Octadecylamine 0.2% Wt.Mineral lubricating oil (SAE 5W) Balance.

COMPOSITION D Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble) 0.3% SA. Ca diwax benzene sulfonate (oil-soluble) 0.5% SA.Cocoamine 0.4% Wt. Mineral lubricating oil (SAE 30) Balance.

COMPOSITION E Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble) 0.3% SA. Ca petroleum sulfonate (oil-soluble) 0.4% SA.Octadecylamine 0.1% wt. a g 55 25 sebacate 50:50 mixture Balance.

COMPOSITION F Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble) 0.3% SA. Ca petroleum sulfonate (oil-soluble) 0.1% SA,Octadecylamine 0.1% wt. Zn methylcyclohexylthiophosphate 1.49% wt.Mineral lubricating oil (SAE 5W) Balance.

COMPOSITION G Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble) 0.3% SA. Ca petroleum sulfonate (oil-soluble) 0.1% SA.Octadecylamine 0.1% wt. Ethylene bis-tolylsulfide 1.5% wt. Minerallubricating oil (SAE 5W) Balance.

COMPOSITION H Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble, M.W. 900- p 1, 100) 0.3% SA. Ca petroleum sulfonate (oilsoluble) 0.1% SA. Stearamide 0.1% wt. Mineral lubricating oil (SAE 5W)Balance.

COMPOSITION I Ca salt of octyl phenol-formaldehyde condensation product(oil-soluble) 0.3% SA. Ca petroleum sulfonate (oil-soluble) 0.1% SA.Stearamide 0.1% wt. Zn methylcyclohexylphosphate 1.49% wt. Minerallubricating oil (SAE 30) Balance.

To illustrate the pronounced improvement obtained in the followingcompositions were tested in a CFR engine under the following engine testconditions and the resultsare recorded below:

Test conditions Wear 011 (Jonsumption Speed, r.p.m 1, 600 1, 800 Time,hrs 40 60 Load, p.s.i 83 75 Jacket temp., F 77 210 Oil temp., 11..- 85M5 Comp. ratio 6 6 taining 0.4% SA Ca petroleum sulfonate, 0.3% SA Casalt of octylphenol-formaldehyde condensation product and 0.2% by weightof phenyl-alpha-naphthylamine), Composition 4 (Mineral oil containing0.3% SA Ca salt of octylphenol-formaldehyde condensation product and0.1% Octadecylamine); Composition 5, (Mineral oil containing 0.1% SA Capetroleum sulfonate and 0.3% SA preventing engine wear and reduction ofoil consumption, 7

Ca salt of octylphenol-formaldehyde condensation product and 0.5%Octadecylamine), were tested under the above test conditions. WithCompositions A, F and H wear reduction of over 50% over Composition 1and above 50% to 75% over Compositions 2, 3, 4 and 5 was noted. Alsowith Compositions A, F and H, about 60% to reduction in oil consumptionwas noted whereas with compositions 2, 3, 4 and 5 no reduction in oilconsumption was noted.

In addition to the addtives already described lubricating oilcompositions contemplated herein may contain other agents, such aspour-point depressants, oiliness agents, blooming agents, compounds forenhancing the viscosity index of the lubricating oil, peptizing agents,etc.

This application is a continuation-in-part of our copending patentapplication Serial No. 366,560, filed June 7, 1953, now abandoned.

We claim as our invention:

1. A lubricating oil composition consisting essentially of a majoramount of a mineral lubricating oil and containing from about 0.1% toabout 6% by weight each of oil-soluble calcium petroleum sulfonate andoil-soluble calcium salt of sulfur-free octylphenol-formaldehydecondensation product and from about 0.01% to about 0.2% by Weight of anoil-soluble alkylamine selected from the group consisting of primary andsecondary dodecylamine, tetra decylamine, hexadecylamine andOctadecylamine.

2. A lubricating oil composition consisting essentially of a majoramount of a mineral lubricating oil containing from about 0.1% to about6% by weight each of oil-soluble calcium petroleum sulfonate andoil-soluble calium salt of sulfur-free octylphenol-formaldehydecoudensation product and from about 0.05% to about 0.1% by weight ofOctadecylamine.

References Cited in the file of this patent UNITED STATES PATENTS2,375,222 Griflin et a1. May 8, 1945 2,402,448 Richards June 18, 19462,420,068 Duncan et al. May 6, 1947 2,684,292 Caron et a1. July 20, 19542,758,086 Stuart et al. Aug. 7, 1956 OTHER REFERENCES CRC Handbook,1946, Coordinating Research Council, Inc. Pub. by Little and Ives. Co.(N.Y.), 1946.

1. A LUBRICATING OIL COMPSOITION CONSISTING ESSENTIALLY OF A MAJORAMOUNT OF A MINERAL LUBRICATING OIL AND CONTAINING FROM ABOUT 0.1% TOABOUT 6% BY WEIGHT EACH OF OIL-SOLUBLE CALCIUM PETROLEUM SULFONATE ANDOIL SOLUBLE CALCIUM SALT OF SULFUR-FREE OCTYLPHENOL-FORMALDEHYDECONDENSATION PRODUCT AND FROM ABOUT 0.01% TO ABOUT 0.2% BY WEIGHT OF ANOIL-SOLUBLE ALKYLAMINE SELECTED FROM THE GROUP CONSISTING OF PRIMARY ANDSECONDARY DODECYLAMINE TETRA DECYLAMINE, HEXADECYLAMINE ANDOCTADECYLAMINE.